The subject of the invention is novel dimethylenedioxybenzenes comprising at least one cationic group Z, Z being chosen from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated ring, and aliphatic chains comprising at least one quaternized unsaturated ring, their use as oxidation dye precursor for the oxidation dyeing of keratinous fibres, dyeing compositions containing them, as well as the oxidation dyeing methods using them.
It is known to dye keratinous fibres, and in particular human hair, with dyeing compositions containing oxidation dye precursors, in particular para-phenylenediamines, ortho- or para-aminophenols, heterocyclic compounds such as diaminopyrazole derivatives, generally called oxidation bases. Oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds which, combined with oxidizing products, can give rise, by a process of oxidative condensation, to coloured and colouring compounds.
It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or colour modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as for example indolic couplers.
The variety of the molecules used in oxidation bases and couplers makes it possible to obtain a rich palette of colours.
The so-called xe2x80x9cpermanentxe2x80x9d colour obtained using these oxidation dyes must moreover meet a number of requirements. Thus, it must be without drawbacks from the toxicological point of view, it must make it possible to obtain shades in the desired intensity and exhibit good resistance to external agents (light, adverse weather conditions, washing, permanent waving, perspiration, rubbing).
The dyes must also make it possible to cover grey hair, and be the least selective possible, that is to say make it possible to obtain the smallest possible differences in colour right along the same keratinous fibre, which may indeed be differently sensitized (i.e. damaged) between its tip and its root.
However, the Applicant has now just discovered, completely unexpectedly and surprisingly, that a novel family of dimethylenedioxybenzenes of formula (I) defined below, comprising at least one cationic group Z, Z being chosen from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated ring, and aliphatic chains comprising at least one quaternized unsaturated ring, is not only suitable for use as oxidation dye precursor for oxidation dyeing, but, in addition, that it makes it possible to obtain dyeing compositions leading to intense colours, in a very broad palette of shades and exhibiting excellent properties of resistance to different treatments to which the keratinous fibres may be subjected.
These discoveries form the basis of the present invention.
The first subject of the invention is therefore dimethylenedioxybenzenes of the following formula (I), and their addition salts with an acid: 
in which:
B is a linking arm which represents a linear or branched alkyl chain preferably comprising from 1 to 14 carbon atoms, which may be interrupted by one or more groups Z as defined below and/or by one or more heteroatoms such as oxygen, sulphur or nitrogen atoms, and optionally substituted with one or more hydroxyl or C1-C6 alkoxy radicals, and which may carry one or more ketone functions;
Ra, Rb, Rxe2x80x2a and Rxe2x80x2b, which are identical or different, may represent a hydrogen atom, a C1-C6 alkyl radical, a C1-C6 hydroxyalkyl radical, or form in pairs, together with the carbon atom to which they are attached, a 5-, 6- or 7-membered saturated carbon ring;
R1, Rxe2x80x21, R2, Rxe2x80x22, R3 and Rxe2x80x23, which may be identical or different, represent a hydrogen atom; a halogen atom; one of the two valences of a linking arm B, a group Z as defined below; a group A2 as defined below; a group A2xe2x80x2 as defined below; a (C1-C6)alkylcarbonyl radical; an amino(C1-C6)alkylcarbonyl radical; an N-Z-amino(C1-C6)alkylcarbonyl radical; an N-(C1-C6)alkylamino(C1-C6)alkylcarbonyl radical; an N,N-di(C1-C6 alkyl)amino(C1-C6)alkylcarbonyl radical; an amino(C1-C6)alkylcarbonyl(C1-C6)alkyl radical; an N-Z-amino(C1-C6)alkylcarbonyl(C1-C6)alkyl radical; an N-(C1-C6 alkyl)amino(C1-C6)alkylcarbonyl(C1-C6)alkyl radical; an N,N-di(C1-C6 alkyl)amino(C1-C6)alkylcarbonyl(C1-C6)alkyl radical; a carboxyl radical; a (C1-C6)alkylcarboxyl radical; a (C1-C6)alkylsulphonyl radical; an aminosulphonyl radical; an N-Z-aminosulphonyl radical; an N-(C1-C6 alkyl)aminosulphonyl radical; an N,N-di(C1-C6 alkyl)aminosulphonyl radical; an aminosulphonyl(C1-C6)alkyl radical; an N-Z-aminosulphonyl(C1-C6)alkyl radical; an N-(C1-C6 alkyl)aminosulphonyl(C1-C6)alkyl radical; an N,N-di(C1-C6 alkyl)aminosulphonyl(C1-C6)alkyl radical; a carbamyl radical; an N-(C1-C6 alkyl)carbamyl radical; an N,N-di(C1-C6 alkyl)carbamyl radical; a carbamyl(C1-C6)alkyl radical; an N-(C1-C6 alkyl)carbamyl(C1-C6)alkyl radical; an N,N-di(C1-C6 alkyl)carbamyl(C1-C6)alkyl radical; a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a (C1-C6)alkoxy(C1-C6)alkyl radical; a C1-C6 trifluoroalkyl radical; a cyano radical; a group OR6, ORxe2x80x26, SR6 or SRxe2x80x26; a C1-C6 aminoalkyl radical in which the alkyl is unsubstituted or substituted with one or more hydroxyl radicals; an amino(C1-C6)alkyl radical in which the alkyl is unsubstituted or substituted with one or more hydroxyl radicals and in which the amine is substituted with one or two radicals, which are identical or different, chosen from the alkyl, C1-C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, (C1-C6)alkylcarbonyl, carbamyl, N-(C1-C6 alkyl)carbamyl or N,N-di(C1-C6 alkyl)carbamyl, C1-C6)alkylsulphonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl or thiocarbamyl radicals, or from the groups Z as defined below, or which can form together, with the nitrogen atom to which they are attached, a 5- or 6-membered ring, containing carbon or containing one or more heteroatoms;
R6 and Rxe2x80x26, which may be identical or different, denote one of the two valences of a linking arm B; a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a group Z as defined below; a (C1-C6)alkoxy(C1-C6)alkyl radical; an aryl radical; a benzyl radical; a C1-C6 carboxyalkyl radical; a (C1-C6)alkylcarboxy(C1-C6)alkyl radical; a C1-C6 cyanoalkyl radical; a C1-C6 carbamylalkyl radical; an N-(C1-C6 alkyl)carbamyl(C1-C6)alkyl radical; an N,N-di(C1-C6 alkyl)carbamyl(C1-C6)alkyl radical; a C1-C6 trifluoroalkyl radical; a C1-C6 aminosulphonylalkyl radical; a C1-C6 N-Z-aminosulphonylalkyl radical; an N-(C1-C6 alkyl)aminosulphonyl(C1-C6)alkyl radical; an N,N-di(C1-C6 alkyl)aminosulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylsulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylsulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylcarbonyl(C1-C6)alkyl radical; an amino(C1-C6)alkyl radical; an amino(C1-C6)alkyl radical in which the alkyl is unsubstituted or substituted with one or more hydroxyl radicals and in which the amine is substituted with one or two radicals, which are identical or different, chosen from the (C1-C6)alkylmonohydroxy(C1-C6)alkyl, polyhydroxy(C2-C6)alkyl, (C1-C6)alkylcarbonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, carbamyl, N-(C1-C6 alkyl)carbamyl, N,N-di(C1-C6 alkyl)carbamyl, thiocarbamyl and (C1-C6)alkylsulphonyl radicals, and among the groups Z as defined below; or which can form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing carbon or containing one or more heteroatoms;
A1 represents a group xe2x80x94NR4R5 or a hydroxyl radical;
Axe2x80x21 represents a group xe2x80x94NRxe2x80x24Rxe2x80x25 or a hydroxyl radical;
A2 represents a group xe2x80x94NRxe2x80x34Rxe2x80x35 or a hydroxyl radical;
Axe2x80x22 represents a group xe2x80x94NRxe2x80x2xe2x80x34Rxe2x80x2xe2x80x35 or a hydroxyl radical;
R4, R5, Rxe2x80x24, Rxe2x80x25, Rxe2x80x34, Rxe2x80x35, Rxe2x80x2xe2x80x34 and Rxe2x80x2xe2x80x35, which are identical or different, represent one of the two valences of a linking arm B; a hydrogen atom; a group Z as defined below; a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a (C1-C6)alkoxy(C1-C6)alkyl radical; an aryl radical; a benzyl radical; a C1-C6 cyanoalkyl radical; a C1-C6 carbamylalkyl radical; an N-(C1-C6 alkyl)carbamyl(C1-C6)alkyl radical; an N,N-di(C1-C6 alkyl)carbamyl(C1-C6)alkyl radical; a C1-C6 thiocarbamylalkyl radical; a C1-C6 trifluoroalkyl radical; a C1-C6 sulphoalkyl radical; a (C1-C6)alkylcarboxy(C1-C6)alkyl radical; a (C1-C6)alkylsulphinyl(C1-C6)alkyl radical; a C1-C6 aminosulphonylalkyl radical; a C1-C6 N-Z-aminosulphonylalkyl radical; an N-(C1-C6 alkyl)aminosulphonyl(C1-C6)alkyl radical; an N,N-di(C1-C6 alkyl)aminosulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylcarbonyl(C1-C6)alkyl radical; a C1-C6 aminoalkyl radical in which the alkyl is unsubstituted or substituted with one or more hydroxyl radicals; a C1-C6 aminoalkyl radical in which the alkyl is unsubstituted or substituted with one or more hydroxyl radicals and in which the amine is substituted with one or two radicals, which are identical or different, chosen from the C1-C6 alkyl, C1-C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, (C1-C6)alkylcarbonyl, carbamyl, N-(C1-C6 alkyl)carbamyl, N,N-di(C1-C6 alkyl)carbamyl, (C1-C6)alkylsulphonyl, formyl, trifluoro(C1-C6 alkyl)carbonyl, (C1-C6)alkylcarboxyl and thiocarbamyl radicals, or from the groups Z as defined below, or which can form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing carbon or containing one or more heteroatoms;
Z is chosen from the unsaturated cationic groups of the following formulae (II) and (III), and the saturated cationic groups of the following formula (IV): 
xe2x80x83in which
D is a linking arm which represents a linear or branched alkyl chain preferably comprising from 1 to 14 carbon atoms, which may be interrupted by one or more heteroatoms such as oxygen, sulphur or nitrogen atoms, and which may be substituted with one or more hydroxyl or C1-C6 alkoxy radicals, and which may carry one or more ketone functions;
the members E, G, J, L and M, which are identical or different, represent a carbon, oxygen, sulphur or nitrogen atom;
n is an integer between 0 and 4 inclusive;
m is an integer between 0 and 5 inclusive;
the radicals R, which are identical or different, represent one of the two valences of a linking arm B; a second group Z which is identical to or different from the first group Z; a halogen atom; a hydroxyl radical; a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a nitro radical; a cyano radical; a C1-C6 cyanoalkyl radical; a C1-C6 alkoxy radical; a tri(C1-C6 alkyl)silane(C1-C6)alkyl radical; an amido radical; an aldehydo radical; a carboxyl radical; a C1-C6 alkylcarbonyl radical; a thio radical; a C1-C6 thioalkyl radical; a (C1-C6)alkylthio radical; an amino radical; an amino radical protected with a (C1-C6)alkylcarbonyl, carbamyl or (C1-C6)alkylsulphonyl radical; a group NHRxe2x80x3 or NRxe2x80x3Rxe2x80x2xe2x80x3 in which Rxe2x80x3 and Rxe2x80x2xe2x80x3, which are identical or different, represent a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical or a C2-C6 polyhydroxyalkyl radical;
R7 represents a C1-C6 alkyl radical; one of the two valences of a linking arm B; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a C1-C6 cyanoalkyl radical; a tri(C1-C6 alkyl)silane(C1-C6)alkyl radical; a (C1-C6)alkoxy(C1-C6)alkyl radical; a C1-C6 carbamylalkyl radical; a (C1-C6)alkylcarboxy(C1-C6)alkyl radical; a benzyl radical; or a second group Z which is identical or different from the first group Z;
R8, R9 and R10 which are identical or different, represent one of the two valences of a linking arm B; a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a (C1-C6)alkoxy(C1-C6)alkyl radical; a C1-C6 cyanoalkyl radical; an aryl radical; a benzyl radical; a C1-C6 amidoalkyl radical; a tri(C1-C6 alkyl)silane(C1-C6)alkyl radical; or a C1-C6 aminoalkyl radical in which the amine is protected by a (C1-C6)alkylcarbonyl, carbamyl or (C1-C6)alkylsulphonyl radical; two of the radicals R8, R9 and R10 may also form together, with the nitrogen atom to which they are attached, a 5- or 6-membered saturated ring containing carbon or containing one or more heteroatoms such as for example a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring, it being possible for the said ring to be unsubstituted or substituted with a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a nitro radical, a cyano radical, a C1-C6 cyanoalkyl radical, a C1-C6 alkoxy radical, a tri(C1-C6 alkyl)silane(C1-C6)alkyl radical, an amido radical, an aldehydo radical, a carboxyl radical, a C1-C6 ketoalkyl radical, a thio radical, a C1-C6 thioalkyl radical, a (C1-C6)alkylthio radical, an amino radical, an amino radical protected by a (C1-C6)alkylcarbonyl, carbamyl or (C1-C6)alkylsulphonyl radical;
xe2x80x83one of the radicals R8, R9 and R10 can also represent a second group Z which is identical to or different from the first group Z;
R11 represents one of the two valences of a linking arm B; a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a C1-C6 aminoalkyl radical, a C1-C6 aminoalkyl radical in which the amine is protected with a (C1-C6)alkylcarbonyl, carbamyl or (C1-C6)alkylsulphonyl radical; a C1-C6 carboxyalkyl radical; a C1-C6 cyanoalkyl radical; a C1-C6 carbamylalkyl radical; a C1-C6 trifluoroalkyl radical; a tri(C1-C6 alkyl)silane(C1-C6)alkyl radical; a C1-C6 sulphonamidoalkyl radical; a (C1-C6)alkylcarboxy(C1-C6)alkyl radical; a (C1-C6)alkylsulphinyl(C1-C6)alkyl radical; a (C1-C6)alkylsulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylketo(C1-C6)alkyl radical; an N-(C1-C6 alkyl)carbamyl(C1-C6)alkyl radical; an N-(C1-C6 alkyl)sulphonamido(C1-C6)alkyl radical;
a and y are integers equal to 0 or 1; with the following conditions:
xe2x80x83in the unsaturated cationic groups of formula (II):
when a=0, the linking arm D is attached to the nitrogen atom,
when a=1, the linking arm D is attached to one of the members E, G, J or L,
y can only take the value 1:
1) when the members E, G, J and L simultaneously represent a carbon atom and when the radical R7 is carried by the nitrogen atom of the unsaturated ring; or alternatively
2) when at least one of the members E, G, J and L represents a nitrogen atom to which the radical R7 is attached;
in the unsaturated cationic groups of formula (III):
when a=0, the linking arm D is attached to the nitrogen atom,
when a=1, the linking arm D is attached to one of the members E, G, J, L or M,
y can only take the value 1 when at least one of the members E, G, J, L and M represents a divalent atom, and when the radical R7 is carried by the nitrogen atom of the unsaturated ring;
xe2x80x83in the cationic groups of formula (IV):
when a=0, then the linking arm D is attached to the nitrogen atom carrying the radicals R8 to R10,
when a=1, then two of the radicals R8 to R10 form together with the nitrogen atom to which they are attached a 5- or 6-membered saturated ring as defined above, and the linking arm D is carried by a carbon atom of the said saturated ring;
Xxe2x88x92 represents a monovalent or divalent anion and is preferably chosen from a halogen atom such as chlorine, bromine, fluorine or iodine, a hydroxide, a hydrogen sulphate or a (C1-C6)alkyl sulphate such as for example a methyl sulphate or an ethyl sulphate;
it being understood that:
the number of cationic groups Z is at least equal to 1.
As indicated above, the colours obtained with the oxidation dyeing composition containing one or more compounds of formula (I) in accordance with the invention are intense and make it possible to obtain shades in a very broad palette of colours. They exhibit, furthermore, excellent properties of resistance against the action of the various external agents (light, adverse weather conditions, washing, permanent waving, perspiration, rubbing). These properties are particularly remarkable in particular as regards the resistance of the colours obtained to the action of light, washing and perspiration.
In formulae (I), (II), (III) and (IV) above, the alkyl and alkoxy radicals may be linear or branched.
Among the carbon-containing rings which can be formed conjointly by the radicals Ra and Rb or Rxe2x80x2a and Rxe2x80x2b, there may be particularly mentioned the pentane, hexane and heptane rings.
Among the rings of the unsaturated groups Z of formula (II) above, there may be mentioned in particular, by way of example, the pyrrole, imidazole, pyrazole, oxazole, thiazole and triazole rings.
Among the rings of the unsaturated groups Z of formula (III) above, there may be mentioned in particular, by way of example, the pyridine, pyrimidine, pyrazine, oxazine and triazine rings.
The compounds of formula (I) above are preferably chosen from:
3-[2-(6-aminobenzo[1,3]dioxol-5-ylamino)ethyl]-1-(4-{3-[2-(6-aminobenzo[1,3]dioxol-5-ylamino)ethyl]-3H-imidazol-1-ium}butyl)-3H-imidazol-1-ium dichloride;
3-[2-(6-hydroxybenzo[1,3]dioxol-5-ylamino)ethyl]-1-(4-{3-[2-(6-hydroxybenzo[1,3]dioxol-5-ylamino)ethyl]-3H-imidazol-1-ium}butyl)-3H-imidazol-1-ium dichloride;
3-[2-(6-methoxybenzo[1,3]dioxol-5-ylamino)ethyl]-1-(4-{3-[2-(6-methoxybenzo[1,3]dioxol-5-ylamino)ethyl]-3H-imidazol-1-ium}butyl)-3H-imidazol-1-ium dichloride;
1,3-bis[3-(6-aminobenzo[1,3]dioxol-5-yloxy)propyl]-3H-imidazol-1-ium chloride;
3-[2-(6-aminobenzo[1,3]dioxol-5-yloxy)ethyl]-1-(4-{3-[2-(6-aminobenzo[1,3]dioxol-5-yloxy)ethyl]-3H-imidazol-1-ium}butyl)-3H-imidazol-1-ium dichloride;
3-[3-(6-aminobenzo[1,3]dioxol-5-yloxy)propyl]-1-(4-{3-[3-(6-aminobenzo[1,3]dioxol-5-yloxy)propyl]-3H-imidazol-1-ium}butyl)-3H-imidazol-1-ium dichloride;
3-[2-(6-aminobenzo[1,3]dioxol-5-yloxy)ethyl]-1-(3-{[2-(6-aminobenzo[1,3]dioxol-5-yloxy)ethyl]dimethylammonium}propyl)-3H-imidazol-1-ium dichloride;
[2-(6-aminobenzo[1,3]dioxol-5-yloxy)ethyl]-(2-{[2-(6-aminobenzo[1,3]dioxol-5-yloxy)ethyl]dimethylammonium}ethyl)dimethylammonium dichloride;
and their addition salts with an acid.
The addition salts with an acid of the compounds of formula (I) in accordance with the invention are preferably chosen from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.
The compounds of formula (I) in accordance with the invention can be easily obtained, according to methods well known in the state of the art, for example by reducing the corresponding cationic nitro compounds when these compounds contain an amino group.
This reducing step (production of a primary aromatic amine) followed or otherwise by salification, is in general, for convenience, the last step of the synthesis.
This reduction can take place earlier in the sequence of reactions leading to the preparation of the compounds of formula (I), and according to well known methods; it is then necessary to xe2x80x9cprotectxe2x80x9d the primary amine created (for example by an acetylation, formylation or benzenesulphonation step, and the like), then carry out the desired substitutions or modifications (including the quaternization) and finish by the xe2x80x9cdeprotectionxe2x80x9d (in general in acid medium) of the amine function.
Likewise, the phenolic function may be protected according to well-known methods with a benzyl radical (xe2x80x9cdeprotectionxe2x80x9d by catalytic reduction) or with an acetyl or mesyl radical (xe2x80x9cdeprotectionxe2x80x9d in acid medium).
These cationic dimethylenedioxybenzene compounds are obtained by methods well known in the state of the art, for example by:
condensation of two molecules of a methylenedioxybenzene compound carrying a haloalkyl radical with one molecule of a compound carrying two tertiary amine radicals separated by a linking arm B as defined in the formula (I) described above, or alternatively,
(a) condensation of one molecule of a methylenedioxybenzene compound carrying a tertiary amine radical with one molecule of a compound carrying two halogen radicals separated by a linking arm B as defined in the formula (I) described above, and (b) condensation of a second molecule of a methylenedioxybenzene compound different from the first and it too carrying a tertiary amine radical, or alternatively,
(a) condensation of one molecule of a methylenedioxybenzene compound carrying a haloalkyl radical with one molecule of a compound carrying two tertiary amine radicals separated by a linking arm B as defined in the formula (I) described above, and (b) condensation of a second molecule of a methylenedioxybenzene compound different from the first and it too carrying a haloalkyl radical, or alternatively,
condensation of one molecule of a methylenedioxybenzene compound carrying a tertiary amine radical with one molecule of a methylenedioxybenzene compound carrying a haloalkyl radical.
The haloalkyl radicals carried by the intermediate dimethylenedioxybenzene compounds can be prepared by known state of the art methods in one or more steps, for example by condensation of a dihaloalkyl compound with an amine or a hydroxyl, or by halogenation of a hydroxyalkyl chain.
When the synthesis is finished, the compounds of formula (I) in accordance with the invention can, where appropriate, be recovered by well known state of the art methods such as crystallization or distillation.
Another subject of the invention is the use of the compounds of formula (I) in accordance with the invention as oxidation dye precursor for the oxidation dyeing of keratinous fibres, and in particular human keratinous fibres such as hair.
The subject of the invention is also a composition for the oxidation dyeing of keratinous fibres and in particular human keratinous fibres such as hair, characterized in that it comprises, as oxidation dye precursor, in a medium appropriate for dyeing, at least one compound of formula (I) in accordance with the invention.
The compound(s) of formula (I) in accordance with the invention preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dyeing composition, and still more preferably from 0.005 to 6% by weight approximately of this weight.
The medium appropriate for dyeing (or carrier) generally consists of water or of a mixture of water and of at least one organic solvent. As organic solvent, there may be mentioned for example lower C1-C4 alkanols, such as ethanol and isopropanol; glycerol, glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, monomethyl ether of propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar products and mixtures thereof.
The solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dyeing composition, and still more preferably between 5 and 30% by weight approximately.
The pH of the dyeing composition in accordance with the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalinizing agents normally used in dyeing keratinous fibres.
Among the acidifying agents, there may be mentioned, by way of example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid and sulphonic acids.
Among the alkalinizing agents, there may be mentioned, by way of example, aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines as well as derivatives thereof, sodium or potassium hydroxides and the compounds of the following formula (V): 
in which W is a propylene residue optionally substituted by an hydroxyl group or a C1-C6 alkyl radical; R12, R13, R14 and R15, which are identical or different, represent a hydrogen atom, a C1-C6 alkyl or C1-C6 hydroxyalkyl radical.
The dyeing composition in accordance with the invention may also contain, in addition to the compound(s) of formula (I) defined above, at least one oxidation base which may be chosen from the oxidation bases conventionally used in oxidation dyeing and among which there may be mentioned in particular para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Among the para-phenylenediamines, there may be mentioned more particularly, by way of example, para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-chloroaniline, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(xcex2-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl-xcex2-hydroxyethyl)-para-phenylenediamine, N-(xcex2,xcex3-dihydroxypropyl)-para-phenylenediamine, N-(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-xcex2-hydroxyethyloxy-para-phenylenediamine, 2-xcex2-acetylaminoethyloxy-para-phenylenediamine, N-(xcex2-methoxyethyl)-para-phenylenediamine, and their addition salts with an acid.
Among the bisphenylalkylenediamines, there may be mentioned more particularly, by way of example, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diaminopropanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3xe2x80x2-methylphenyl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their addition salts with an acid.
Among the para-aminophenols, there may be mentioned more particularly, by way of example, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(xcex2-hydroxyethylaminomethyl)phenol, and their addition salts with an acid.
Among the ortho-aminophenols, there may be mentioned more particularly, by way of example, 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol and their addition salts with an acid.
Among the heterocyclic bases, there may be mentioned more particularly, by way of example, the pyridine derivatives, the pyrimidine derivatives and the pyrazole derivatives.
Among the pyridine derivatives, there may be mentioned more particularly the compounds described for example in Patents GB 1,026,978 and GB 1,153,196, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(xcex2-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and their addition salts with an acid.
Among the pyrimidine derivatives, there may be mentioned more particularly the compounds described for example in German Patent DE 2,359,399 or in Japanese Patents JP 88-169,571 and JP 91-10659 or Patent Application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and the pyrazolopyrimidine derivatives such as those mentioned in Patent Application FR-A-2,750,048 and among which there may be mentioned pyrazolo[1,5-a]-pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1,5-a]-pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine; 3-aminopyrazolo[1,5-a]pyrimidin-7-ol; 3-aminopyrazolo[1,5-a]pyrimidin-5-ol; 2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxyethyl)-amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxyethyl)amino]ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]pyrimidine, their tautomeric forms, when a tautomeric equilibrium exists, and their addition salts with an acid.
Among the pyrazole derivatives, there may be mentioned more particularly the compounds described in Patents DE 3,843,892, DE 4,133,957 and Patent Applications WO 94/08969, WO 94/08970, FR-A-2,733,749 and DE-195 43 988 such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4xe2x80x2-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(xcex2-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4xe2x80x2-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2xe2x80x2-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(xcex2-hydroxyethyl)amino-1-methylpyrazole, and their addition salts with an acid.
When they are used, these oxidation bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dyeing composition, and still more preferably from 0.005 to 6% by weight approximately of this weight.
The oxidation dyeing compositions in accordance with the invention may also contain one or more couplers and/or one or more direct dyes, in particular for modifying the shades or enriching them with glints.
The couplers which can be used in the oxidation dyeing compositions in accordance with the invention may be chosen from the couplers conventionally used in oxidation dyeing and among which there may be mentioned in particular meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers such as for example indole derivatives, indoline derivatives, pyridine derivatives and pyrazolones, and their addition salts with an acid.
These couplers are more particularly chosen from 2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)benzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, xcex1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, and their addition salts with an acid.
When they are present, these couplers preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dyeing composition and still more preferably from 0.005 to 5% by weight approximately of this weight.
In general, the addition salts with an acid which can be used in the context of the invention (oxidation bases and couplers) are in particular chosen from the hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.
The dyeing composition in accordance with the invention may also contain various adjuvants which are conventionally used in hair-dyeing compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickening agents, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example silicones, film-forming agents, preservatives and opacifying agents.
Of course, persons skilled in the art will be careful to choose this or these possible additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition in accordance with the invention are not, or not substantially, impaired by the addition(s) envisaged.
The dyeing composition according to the invention may be provided in various forms, such as in the form of liquids, creams, gels or in any other form appropriate for carrying out a dyeing of keratinous fibres, and in particular human hair.
The subject of the invention is also a method of dyeing keratinous fibres, and in particular human keratinous fibres such as hair, using the dyeing composition as defined above.
The subject of the invention is also a method of oxidation dyeing of keratinous fibres, and in particular human keratinous fibres such as hair, using the dyeing composition as defined above.
According to this method, at least one dyeing composition as defined above is applied to the fibres for a period sufficient to develop the desired colour, either with air or with the aid of an oxidizing agent. The dyeing composition may optionally contain oxidation catalysts, in order to accelerate the oxidation process.
According to a first embodiment of the method of the invention, the dyeing of the fibres may be carried out without addition of an oxidizing agent, solely by contact with atmospheric oxygen.
According to second embodiment of the method of the invention, and in particular when the dyeing composition in accordance with the invention contains one or more oxidation bases and/or one or more couplers, at least one dyeing composition as defined above is applied to the fibres, the colour being developed at acidic, neutral or alkaline pH with the aid of an oxidizing agent which is added to the dyeing composition just at the time of use or which is present in an oxidizing composition applied simultaneously or sequentially in a separate manner.
According to this second embodiment of the dyeing method of the invention, the dyeing composition described above is preferably mixed, at the time of use, with an oxidizing composition containing, in a medium appropriate for dyeing, at least one oxidizing agent present in a sufficient quantity to develop a colour. The mixture obtained is then applied to the keratinous fibres and allowed to act for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which they are washed with shampoo, rinsed again and dried.
The oxidizing agent present in the oxidizing composition as defined above may be chosen from oxidizing agents conventionally used for the oxidation dyeing of keratinous fibres, and among which there may be mentioned hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates and enzymes such as peroxidases, laccases, tyrosinases and oxidoreductases among which there may be mentioned in particular pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases and uricases.
The pH of the oxidizing composition containing the oxidizing agent as defined above is such that after mixing with the dyeing composition, the pH of the resulting composition applied to the keratinous fibres preferably varies between 3 and 12 approximately, and still more preferably between 5 and 11. It is adjusted to the desired value by means of acidifying or alkalinizing agents normally used for dyeing keratinous fibres and as defined above.
The oxidizing composition as defined above may also contain various adjuvants conventionally used in hair-dyeing compositions and as defined above.
The composition which is finally applied to the keratinous fibres may be provided in various forms, such as in the form of liquids, creams, gels, or in any other form appropriate for dyeing keratinous fibres, and in particular human hair.
Another subject of the invention is a multi-compartment device or dyeing xe2x80x9ckitxe2x80x9d or any other multi-compartment packaging system in which a first compartment contains the dyeing composition as defined above and a second compartment contains the oxidizing composition as defined above. These devices may be equipped with a means which makes it possible to deliver the desired mixture onto the hair, such as the devices described in Patent FR-2,586,913 in the name of the Applicant.